Diesel Hydrotreating (DHDT UNIT)

Introduction:
Distillate or Diesel Hydrotreaters, also referred to as Hydro-desulfurization Units, remove organic
sulfur, nitrogen, halide, oxygenate, and metals compounds from diesel boiling range feed.
Hydrotreaters achieve this by passing feed over a bed of hydrotreating catalyst in the presence of
hydrogen and at high temperatures and relatively high pressures. Organic Sulfur and Nitrogen
Compounds must be removed from diesel product to reduce SOX and NOX emissions from diesel
engines during combustion. In the diesel hydrotreating process, organic sulfur, nitrogen, and
oxygen compounds are converted to H2S, Ammonia, and Water, respectively. C4H9SH + H2 →
C4H10 + H2S C5H5N + 5H2 → C5H12 + NH3 C6OH +H2 → C6H12+ H2O

Metal contaminants are trapped on the reactor catalyst surface, which in addition to coking,
deactivates the catalyst overtime and necessitating catalyst change-out. Because these reactions
take place in the presence of hydrogen, hydrotreating also saturates olefin and aromatic
compounds in the feed.

Feed and Feed Pre-Heat

Diesel from numerous units in the refinery e.g. Crude/Vac, FCC, Coker, etc. are combined with makeup
and recycle hydrogen. The combined feed is directed to the feed preheat section of the plant where it is
exchanged with hot reactor effluent to raise the mixture to optimum feed heater inlet
temperature. This decreases the duty (energy) requirement of the fired feed heater-saving on
natural gas or fuel oil which fires the heater. In the fired heater, the feed passes through the fired
heater’s tubes where it is raised to the required reactor inlet temperature to promote the
hydrotreating reactions, 300 to 400C in the unit depicted above.

Reactor
The hydrotreating reactions are exothermic. As a result, a temperature rise is observed across the
reactor catalyst bed. To prevent a runaway, or uncontrolled, extremely high temperature reactions in the
catalyst bed, reactor bed temperatures are closely monitored. A runaway result in extremely high
temperatures that could potentially result in a serious safety hazard for refinery personnel as well as
catalyst and equipment damage as temperatures exceed the specifications of the metallurgy of the
reactor vessel. The refiner has several handles to control the rate of reaction: Feed Quality, H2/HC Ratio
or H2 Makeup, Reactor Temperature, Recycle, Quench, LHSV, and Catalyst.

Feed Quality
Feed quality to the diesel hydrotreater, DHT, varies with the refinery’s current crude mix, the type of
upstream unit feeding the diesel hydrotreater, and the operating mode of the upstream units.
Refinery process units do not operate in a vacuum-they are dependent on the operating mode of the
entire refinery. If the refinery is running sweet crudes, less that .5% sulfur, the amount of sulfur in the
feed to a DHT will be much lower than when the refinery is running sour crude. Another concern is
the amount of crack stock in the feed to the unit. Cracked stock is product from a thermal or catalytic
cracking unit like a delayed coker or FCC. These units process the heavier cuts from the crude unit
like gas oil and residue which contain more difficult to process sulfur, nitrogen organic compounds
as well as a higher amount of metals. Diesel direct from the crude unit, referred to as straight run
diesel, results in a much lower exothermal reaction (temperature rise) across the reactor bed
because 1) it is derived direct from the lower sulfur portion of the crude mix and 2) it contains fewer
olefinic , or unsaturated, straight-chain compounds. Olefins react rapidly with hydrogen (to saturate),
an exothermic reaction that results in a large heat release. Another consideration is operation of the
fractionation sections of the upstream units. If the end point of the light cycle oil, LCO, from the
FCC’s Main Column increases (meaning heavier material is drawn from the diesel/LCO draw from
the column and sent to the DHT), a higher amount of more difficult to hydro treat material will be
sent to the DHT.

H2/HC Ratio
The desulfurization, denitrogenation, and deoxygenation reactions consume hydrogen. Hydrogen, H2,
also saturates olefins and aromatics and prevents coking or condensation of hydrocarbon on
hydrotreating catalyst. Think of coking essentially as hydrocarbons burning and leaving carbon residue
on the active sites of the catalyst preventing catalyst from carrying out the required hydrotreating
reactions or catalyst deactivation. H2/HC ratio is the amount of Makeup+ Recycle Hydrogen divided by
barrels of feed. Hydrogen is a feed source for several units in the refinery. Refineries are often H2
limited or do not have enough hydrogen to meet the needs of all H2 consumers. Hydrogen is
generated in the refinery’s Catalytic Reforming or Steam Methane Reforming Units or purchased from
an outside provider. Hydrogen is costly for the refinery to produce or purchase. As such, the H2 to HC
ratio must be optimized to not only meet the needs of
the hydrotreating reactions and to maintain catalyst life but also to ensure profitability for the
refinery. To prevent waste of Hydrogen, Separator Hydrogen is recycled back to the feed of the
hydrotreater in addition to normal H2 make-up. Some refineries also cascade hydrogen purge from
one hydrotreater to another if the hydrogen content is high enough to meet the units needs.

Reactor Temperature
Reactor Temperature is a variable in daily unit operation as well as long term catalyst activity
monitoring. Operations can control the heater coil outlet temperature of the furnace and quench,
described below. Several thermocouples are inserted throughout the catalyst bed to monitor
catalyst activity and look for hot spots due to channeling and poor catalyst loading. Poor distribution
of hydrocarbon through the bed results from channeling which leads to reactor internals damage or
temperature runaway. The Weight Average Bed Temperature is used by unit engineers to monitor
catalyst deactivation. WABT increases SOR to EOR (Start of Run to End of Run) due to coking or
metals deposition on catalyst. Operators should not operate the unit to WABT in daily operation.
Temperatures from individual thermocouples throughout the catalyst bed should be considered and
monitored for hot spots. Still, because of the distance between thermocouples, it is still possible to
have undetected hot spots.

Recycle
Recycling hydrotreated product from the fractionation section back to the feed can also be used to
control the severity of hydrotreating operation. Recycling back the product reduces the amount of
highly contaminated and thus highly reactive feed to the unit. However, this also limits the
capacity or the amount of feed that can be processed in the unit.

Quench
Some Distillate Hydrotreaters have the option of directing hydrogen directly in between beds in
multiple catalyst bed reactors. This hydrogen serves as a means of cooling to the reactors in
high severity operations as well as additional hydrogen for the treating reactions.

LHSV
Liquid Hourly Space Velocity is the volumetric feed rate divided by catalyst volume. Higher
LHSV means a higher feed rate to the unit, means a greater amount of reactive material to the
catalyst, leading to a greater temperature rise across the catalyst. This also leads to earlier
catalyst deactivation.

Catalyst
Hydrotreating Catalyst is typically made of Nickel-Molybdenum. Catalyst is selected by the refinery
to meet a variety of feed, product, and operating goals e.g. typical feed quality and desired operating
severity, medium or Ultra Low Sulfur Diesel operating mode, and length of catalyst life.
Gas Separation
Effluent from the reactor passes through the feed effluent exchanger and enters a fin fan exchanger
where the effluent is cooled to separator temperature, 35C per the above diagram. Organic
Chlorides combined with Ammonia from the denitrogenation reactions to for ammonium salts which
could deposit on the tubes of the fin fan exchanger and, in addition to reduced cooling/heat transfer,
cause lead to corrosion. To prevent this, water is combined with the reactor effluent which washes
the salts away. Once the material is cooled, it enters the separator where the gas phase hydrogen
and light end material (typically C1-C4) is separated or flashes off from the now liquid phase
product. This light end C1-C4 material comes from the small amount of hydrocracking that also
occurs in addition to the hydrotreating reactions. This number is small typically .4-.6 wt% of feed in
most operations. The separator sets the pressure for the unit. Typically two pressure control
schemes are used: 1) the Makeup hydrogen rate is maintained to set unit pressure while the HPS
vent to the sour gas system floats or the HPS vent to the sour gas system is used to control
pressure while make-up hydrogen floats. Remember Hydrogen Partial pressure and pressure of a
DHT is essentially synonymous as it makes the greatest contribution to the pressure of the unit.
Products from the Separator are typically Recycle Hydrogen (Unless Once Through), Vent Gas to
the Sour H2 System or Fuel Gas, Water if there is a water boot, and Liquid Hydrocarbon. The
Recycle Hydrogen in the diagram above is directed to an amine contactor to scrub for H2S and
Ammonia before directing it to the recycle compressor suction to pressure the gas back to the feed
or the reactor as quench. Fractionation The liquid from the separator is directed to the unit’s
fractionation section where products are prepared for downstream units or product blending. The
stripping column depicted above is total condensing meaning that no overhead product is drawn
from the top of the tower other than light ends which are sent to the refinery’s gas plant. This light
end material is removed not only to rid diesel product from any dissolved H2S and ammonia but also
to allow the diesel to meet other specifications like flash for blending. There may also be a naphtha
overhead product that is drawn from the overhead in partial condensing towers (reflux plus product
draw). In the drawing above, the stripping column is heated or reboiled by exchanging a portion of
the bottoms material with hot oil or steam and returning that material to the bottom of the tower.
When feed enters the tower, lighter material vaporizes and rises through the trays of the column
while the heavier material flows down the column. Some valuable diesel product material is also
vaporized and entrained with lighter material which exits the top of the column. This vapor is cooled
to liquid phase in a condenser, collected the overhead receiver. Uncondensed light ends are vented
to sour gas treatment and the heavier liquid is refluxed back to the column to improve separation.
Cooled refluxed higher distillate concentrated liquid flows down over the upper column trays and
comes in contact with rising vapors. Due to vapor liquid equilibrium discussed in earlier posts, heavy
material flows back down the column leading to product purification. Light end material leaves the
overhead drum and is directed to the refinery’s sour gas plant. Product diesel is drawn from the
tower bottoms and sent to tankage or blending.